JPH04175313A - α-olefin polymerization catalyst - Google Patents

Abstract

PURPOSE:To obtain a polymerization catalyst which can keep an ability to perform highly stereoregular polymerization of an alpha-olefin and can exhibit high polymerization activity by mixing activated titanium trichloride with an organometallic compound and a specified organosilicon compound. CONSTITUTION:An alpha-olefin polymerization catalyst comprising activated titanium trichloride (A), an organometallic compound (B) and an organosilicon compound (C) of the formula (wherein R<1> and R<2> are the same or different 1-10 C hydrocarbon groups; OR<4>, OSiR, or SiR ; R<3> is a 1-10 C bivalent hydrocarbon group; and R<4>, R<5> and R<6> are each a 1-10 C hydrocarbon group). The mixing ratio among components A, B and C is such that 0.5-100g mol of component B is used per g atom of the titanium atoms of component A, and 0.001-10mol of component C is used per mol of component B.

Description

[Detailed description of the invention] Industrial applications The present invention relates to a catalyst for α-olefin polymerization.

Conventional technology α-olefin polymerization catalysts made of activated titanium trichloride and organoaluminum compounds contain polymers with different properties from catalysts whose components are so-called magnesium-supported catalysts, in which a titanium compound is supported on a magnesium compound. It has the characteristics of being easy to manufacture and having excellent resistance to poisoning.

However, activated titanium trichloride has problems in that it has lower polymerization activity and slightly lower stereoregularity than magnesium-supported catalysts.

A catalyst that is a combination of a magnesium-supported catalyst and an organoaluminum compound further has a 5i-0-C bond, or a single-ship SiR'R2, (OR')3-, (n = 0
It is known that the use of organosilicon compounds represented by ~2) improves the stereoregularity of the resulting polymer (
For example, JP-A-54-94690, JP-A-56-3620
No. 3, No. 57-63310, No. 58-83016,
Publication No. 62-11705, etc.).

On the other hand, a catalyst consisting of activated titanium trichloride and an organoaluminum compound was further added with R', 5i (OR"), -
By combining organosilicon compounds represented by , (0≦n×4), α-
A method for producing olefin polymers has been proposed (Japanese Unexamined Patent Publication No.
3-238110).

However, despite the improvement in stereoregularity, the polymerization activity may be reduced to less than half of that when no organosilicon compound is used, and the relationship between the improvement in stereoregularity and the decrease in polymerization activity is Depends on the type of.

Problems to be Solved by the Invention An object of the present invention is to provide a polymerization catalyst that maintains high stereoregularity and exhibits high polymerization activity in the polymerization of α-olefins.

Means for Solving the Problems As a result of extensive research into organosilicon compounds to be combined with activated titanium trichloride and organoaluminum compounds, the present inventors have discovered that a cyclic organosilicon compound having an O-3i-0 bond has been developed. The present invention was completed based on the discovery that the object of the present invention can be achieved by using the present invention.

The gist of the invention, that is, the gist of the present invention is as follows: (A) activated titanium trichloride, (B) organometallic compound, and (C) -shipping [provided that R1 and R2 are the same or different carbon atoms of 1 to 10]. Hydrocarbon group, OR', 03iR: or StR:.

R3 is a divalent hydrocarbon group having 1 to 10 carbon atoms;
4, R5 and R6 are each a hydrocarbon group having 1 to 10 carbon atoms. ] An α-olefin polymerization catalyst comprising an organosilicon compound represented by the following.

Activated titanium trichloride Activated titanium trichloride (hereinafter referred to as component A) used in the present invention
That's what it means. ) is a β-type titanium trichloride obtained by reducing titanium tetrachloride with an organoaluminum compound, which is further activated.

Activation of β-type titanium trichloride is performed by treating the titanium trichloride with an electron-donating compound such as an alcohol, ether, ester, lactone, amine, acid halide, acid anhydride, or the like.

Furthermore, activated titanium trichloride is activated with halogen-containing compounds such as titanium tetrachloride, silicon tetrachloride, hydrogen halides, halogenated hydrocarbons, and halogenated organic aluminum compounds, or with halogen elements such as iodine and chlorine. It is also possible to carry out the treatment with an activator, and the treatment with the above-mentioned electron-donating compound can also be carried out in the presence of these activators.

A more detailed method for preparing component A is described, for example, in JP-A-47-34.
No. 478, No. 50-74594, No. 50-74595
No. 50-123090, No. 50-123091, No. 52-107294, No. 53-14192, No. 53-65286, No. 53-65287, etc.

Namely, (1) A method in which TlC14 is reduced with an organoaluminum compound, the obtained solid (hereinafter referred to as the reduced solid) is treated with a complexing agent (electron-donating compound), and further reacted with TiCl4 (Japanese Patent Laid-Open No. 47 -34478).

■ A method in which the reduced solid is treated with a complexing agent and further treated with a monoalkylaluminium cibaride (Japanese Patent Laid-Open No. 50-7
No. 4594).

(2) A method in which the catalyst component obtained in (1) above is further treated with a complexing agent (Japanese Patent Application Laid-open No. 74595/1983).

■ A method in which the reduced solid is treated with a complexing agent and further treated with TlC14 at a temperature of 40°C or less (Japanese Patent Application Laid-open No. 50-1
No. 23090).

(2) A method in which the catalyst component obtained in (1) above is further treated with carbon tetrachloride (Japanese Patent Application Laid-open No. 123091/1983).

■ A method of treating the reduced solid with a chlorinated hydrocarbon having 2 carbon atoms in the presence of a complexing agent (Japanese Unexamined Patent Publication No. 107294/1983)
.

(2) A method in which the reduced solid is treated with a chlorinated hydrocarbon having 3 or more carbon atoms in the presence of a complexing agent (Japanese Patent Laid-Open No. 14192/1983).

■ A method of treating the reduced solid with hydrogenated hydrogen having a carbon number of 2 or more in the presence of a complexing agent and TlC14 (Japanese Patent Application Laid-Open No. 53
-65286).

(2) A method of treating the reduced solid with a chlorinated hydrocarbon having 2 or more carbon atoms in the presence of a complexing agent and AlCl3-ether (
Japanese Patent Publication No. 53-65287).

Component A is prepared as described above, and if necessary, component A may be washed with the above-mentioned inert medium and may be further dried.

In addition, component A further comprises, in the presence of an organoaluminum compound,
Olefin polymers formed in component A upon contact with olefins may also be included. The organoaluminum compound is selected from the organometallic compounds described below that are one of the components of the catalyst of the present invention.

Examples of olefins include ethylene, propylene, 1-butene-1-hexene, 4-methyl-1-pentene, etc.
-Olefins may be used.

Contact with the olefin is preferably carried out in the presence of the inert medium described above. The contact is usually carried out at a temperature of 100°C or less, preferably -10°C to +50°C. The amount of olefin polymer contained in component A is usually 0 per gram of component A.
．． It is 1-100g.

In the contact between component A and the olefin, an electron-donating compound may be present together with the organoaluminum compound. Particularly preferable electron-donating compounds include carboxylic acid esters, amines, and phosphites. Component A that has been in contact with the olefin can be washed, if necessary, with the above-mentioned inert medium or further dried.

Organometallic compoundsOrganometallic compounds (hereinafter referred to as component B) are found in the first part of the periodic table.
It is an organic compound of a group metal to a group II metal. As component B, organic compounds of lithium, magnesium, calcium, zinc and aluminum can be used. Among these, organoaluminum compounds are particularly suitable. As organoaluminum compounds that can be used, - Funagura R, AlX3
-, (wherein R is an alkyl group or an aryl group, X is a halogen atom, an alkoxy group, or a hydrogen atom, and n is an arbitrary number in the range of 1≦n≦3), For example, trialkylaluminum, dialkylaluminum monohalide, monoalkylaluminum civalide, alkylaluminum sesquihalide, dialkylaluminum monoalkoxide, and dialkylaluminum monohydride having 1 to 1 carbon atoms.
Particularly preferred are alkylaluminum compounds having 8, preferably 2 to 6 carbon atoms, or mixtures or complexes thereof. Specifically, trialkylaluminum such as trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, trihexylaluminum, dimethylaluminum chloride, diethylaluminum chloride, diethylaluminum bromide, diethylaluminum iodide, diisobutylaluminum chloride, etc. dialkylaluminum monohalides, methylaluminum dichloride, ethylaluminum dichloride, methylaluminum dichloride, ethylaluminum dichloride, ethylaluminum diiodide, isobutylaluminum dichloride, monoalkylaluminum cybarides, alkylaluminum sesquihalides such as ethylaluminum sesquichloride, Dialkyl aluminum monoalkoxides such as dimethyl aluminum methoxide, diethylaluminum ethoxide, diethylaluminum phenoxide, dipropyl aluminum ethoxide, diisobutyl aluminum ethoxide, diisobutyl aluminum phenoxide, dimethyl aluminum hydride, diethyl aluminum hydride, dipropyl aluminum hydride, diisobutyl aluminum Examples include dialkyl aluminum hydride such as hydride. Two or more of these compounds can be used in combination.

Furthermore, an organic aluminum compound in which two or more pieces of aluminum are bonded via an oxygen atom or a nitrogen atom can also be used. Examples of such compounds include ((1,2H5
) 2AIOA1 (C2H5) 2 .

(C,H,)2^10Al([:,R9)2,
Examples include (C2H,,)2AINAI(口2H,,)22H5.

Examples of organic compounds of metals other than aluminum include diethylmagnesium, ethylmagnesium chloride, diethylzinc, etc., as well as LiA1 (CJs)4. Examples include compounds such as LiAI(CJ+s)-.

Organosilicon Compound The organosilicon compound (hereinafter referred to as component C), which is one component of the catalyst of the present invention, is represented by the above general formula. In training, hydrocarbon groups of R', R'' and OR', 05
iR Chi, SiRg? Examples of the hydrocarbon group for R', R5, and R6 include an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, a cycloalkagenyl group, an aryl group, and an aralkyl group.

Alkyl groups include methyl, ethyl, propyl, 1-
Propyl, butyl, 1-butyl, S-butyl, t-butyl, amyl, l-amyl, t-amyl, hexyl, octyl, 2-ethylhexyl, decyl, etc., and alkenyl groups include vinyl, allyl, propenyl, 1-butenyl, 1-pentenyl, 1-hexenyl, 1-octenyl, 1-dekenyl, 1-methyl-1-pentynyl, 1-methyl-1-hebutenyl, etc., cycloalkyl groups include cyclopentyl, cyclohexyl, Methylcyclohexyl group etc., cycloalkenyl group such as cyclopentenyl, cyclohexenyl, methylcyclohexenyl group, etc., cycloalkagenyl group such as cyclopentagenyl, methylcyclopentagenyl, indenyl group, etc. Examples of the aryl group include phenyl, tolyl, and xylyl groups, and examples of the aralkyl group include benzyl, phenethyl, and 3-phenylpropyl groups.

Further, R3 in the above general formula is a divalent hydrocarbon group, and specific examples include groups represented by the following general formula.

In the above, m is 1 to 10, n, p.

q is 2 to 8, respectively.

Specific examples of the groups (1) to (2) above are as follows.

-C2H,.

Component C is usually -Ship stock R'R25IX2 (X is)
10 gene atoms) and the general formula HOR30
The compound represented by H is reacted with the compound represented by H in the presence of a dehydrohalogenating agent such as pyridine or quinoline.
It can be synthesized by reacting a compound represented by 25I (OR') 2 (R7 is a hydrocarbon group) with a compound represented by the general formula HOR30H in the presence of an acid or base catalyst.

The catalyst of the present invention consists of component A, acid component, and component C.
The composition ratio of component B is 0.5 to 100 g mol, preferably 1 to 100 g mol per 1 gram atom of titanium in component A.
40 g mol, component C is 0.0 for 81 mol of component
It is used in an amount of 0.01 to 10 mol, preferably 0.01 to 1.0 mol.

Polymerization of α-olefins The catalyst of the present invention is suitable for homopolymerization of α-olefins having 3 to 10 carbon atoms or other monoolefins or monoolefins having 3 to 1 carbon atoms.
It is particularly useful as a catalyst for copolymerization with C3 to C6 alpha-olefins, such as propylene, 1-butene, 4-methyl-1-pentene,
It exhibits extremely excellent performance as a catalyst for homopolymerization of 1-hexene, etc., or random and block copolymerization with each other and/or with ethylene.

The polymerization reaction may be performed in either a gas phase or a liquid phase. When polymerizing in a liquid phase, inert carbonization of normal butane, isobutane, normal pentane, isopentane, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, etc. It can be carried out in hydrogen and in liquid monomers. The polymerization temperature is usually in the range of -80°C to +150°C, preferably 40 to 120°C. The polymerization pressure may be, for example, 1 to 60 atmospheres. The molecular weight of the resulting polymer can also be controlled by the presence of hydrogen or other known molecular weight regulators. In addition, the amount of other olefin to be copolymerized with the α-olefin in the copolymerization is usually up to 30% by weight, particularly 0.3 to 15% by weight based on the α-olefin.
Selected within the range of weight %. The polymerization reaction using the catalyst system according to the present invention may be carried out in a continuous or batchwise reaction, and the conditions may be those commonly used. Further, the copolymerization reaction may be carried out in one stage, or may be carried out in two or more stages.

Effects of the Invention The catalyst of the present invention can produce a highly stereoregular polymer in high yield in the polymerization of α-olefins.

EXAMPLES The present invention will be specifically explained by examples and application examples. Note that percentages (%) in the examples are based on weight unless otherwise specified.

The heptane insoluble content (hereinafter abbreviated as HI), which indicates the proportion of crystalline polymer in the polymer, is the residual amount when extracted with boiling n-hebutane for 6 hours using a modified Soxhlet extractor.

Example 1 Preparation of component A (activated titanium trichloride) 21 flasks equipped with a stirrer were placed in a constant temperature water bath kept at 0°C, and 700 mN purified hebutane and 250 mN titanium tetrachloride were added to the flasks. Add and mix. Next, while maintaining the temperature of this hebutane solution of titanium tetrachloride at 0°C, 315 rnl of diethylaluminum chloride,
117-ethylaluminum dichloride and 400r
A mixture consisting of nl of purified hebutane was mixed dropwise over a period of 3 hours. After completion of the dropwise addition, the contents were heated with a stirrer and brought to 65° C. after 1 hour, and further stirred at this temperature for 1 hour to obtain a reduced solid. The resulting reduced solid was separated, washed with purified hepatane, and then incubated at 65°C under reduced pressure for 30
Dry for a minute.

Next, a suspension of 25 g of this reduced solid is dispersed in 100-purified hexachloroethane is prepared, and then an amount of hexachloroethane corresponding to 1 gram mole of hexachloroethane per gram atom of titanium in the reduced solid is added to the suspension. 100 mj2 of hexachloroethane
Add in the form of a solution containing 25 g of hexchloroethane,
Furthermore, per gram atom of titanium in the reduced solid, 0. Di-n-butyl ether in an amount corresponding to 100 g moles was added and mixed with stirring.

Next, this mixed solution was heated to 80° C. while stirring, and after stirring for 5 hours, the obtained solid was 100 ml! Component A was prepared by washing 5 times with butane and drying at 65° C. for 30 minutes.

The above-obtained component A12.
Solution 2 containing 6 mg, 1 mol of diethylaluminium chloride (hereinafter referred to as DEAC) in 1 liter of n-heptane
1 mf of a solution containing 0.2 mol of 2-cyclohexyl-2-methyl-2-silar 1,3-dioxane (hereinafter referred to as CMR5) in 11 mf and n-heptane was mixed and held for 5 minutes. I put it in. Next, 750 ml of hydrogen gas as a molecular weight control agent! and liquid propylene II
After pressurizing the reactor, the temperature of the reaction system was raised to 70° C., and propylene was polymerized for 1 hour. After the polymerization was completed, unreacted propylene was purged to obtain a white polypropylene powder with an HI of 97.2%. The polymerization activity (RT) of the catalyst is 5.7 k
g/g・Component A.

Note that CMR3 was prepared as follows. 150 mA' of dry ether was placed in a reaction vessel and cooled on ice. To this, 47.5 g of cyclohexylmethyldichlorosilane
A mixture of 18.8 g of 1,3-propanediol, 40 g of pyridine and 100 g of dry ether were simultaneously added dropwise with stirring. After the dropwise addition, the mixture was stirred at room temperature for 16 hours. The formed precipitate is filtered,
By distilling the filtrate, 319.9 g of CMR was obtained.

The boiling point was 83°C/0.1 mmHg.

Examples 2 to 4 Propylene was polymerized in the same manner as in Example 1, except that the organic silicon compounds shown in Table 1 were used instead of CMR3, and the results are shown in Table 1.

Comparative Example I Polymerization of propylene was carried out in the same manner as in Example 1, except that CMR3 was not used, and the results are shown in Table 1.

Examples 5 to 7 Example 1 except that triethylaluminum was used instead of DEAC as the organometallic compound, and the compounds shown in Table 1 were used instead of CMR3 as the organosilicon compound.
Polymerization of propylene was carried out in the same manner as above, and the results are shown in Table 1.

Comparative Example 2 Propylene was polymerized in the same manner as in Examples 5 to 8, except that no organosilicon compound was used, and the results are shown in Table 1.

Table 1 Comparative Example 1 □ Comparative Example 2 □ RT HI (kg/g・Component A) (%) 5, 7
97.2 6, 1 97.4 6, 2 97.8 4, 2 96.7 2, 0 97.0 14.3 96.116, 2
96.616,8
95.818, 5 84.3

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a flowchart showing the steps for preparing the catalyst of the present invention.

Claims (1)

[Claims] (A) Activated titanium trichloride, (B) Organometallic compound, and (C) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [However, are R^1 and R^2 the same? Different number of carbons 1-1
0 hydrocarbon groups, OR^4, OSiR^5_3 or S
iR^6_3 and R^3 are divalent hydrocarbon groups having 1 to 10 carbon atoms, and R^4, R^5 and R^6 are each hydrocarbon groups having 1 to 10 carbon atoms. ] An α-olefin polymerization catalyst comprising an organosilicon compound represented by: